Resin from phenol, formaldehyde, saturated and unsaturated hydrocarbons, and rosin



Patented Apr. 20, 1948 3 4 A.

SATURATED AND UNSATURATED HYDRO-e CARBONS, AND ROSIN Brita Bostler and Leopold Bornstein, Wilmington, DeL, assignora to Wilmington Chemical Corporation, Wilmington, Del., a corporation of Delaware N Drawing. Application February 8, 1941, Serial No. 377,268. In Germany May 30, 1938 l This invention relates to improvements in the synthetic resin compositions disclosed in U. 8.

Patent No. 2,247,411 and in the method of making such compositions.

which is incorporated in condensation products,

2 Claims. (Cl.- 260-25) etc., as described in said patent. and is obtained iromwaste products of mineral oil refining, consists essentlally'oi three parts; and'we have further found that these three parts have difler'ent It has been noted that saturated petroleum hy- 5 reactivities, especially in condensation reactions. drocarbons are generally not compatible with syn- These three parts maybe designated (1) the first thetic resins and lacquers and in some instances soluble fraction, (2) the second soluble fraction, if excessive amounts are carried into the conand (3) the insoluble fraction. 0! these, the first densation product, this results in cloudiness in soluble {Bastion isi so(luble i3 ordinary 00mg:- the resin or a separation of the oils. This effect trated s c acd e- 8-, 8 D cenw- 6 may or may not be undesirable depending upon second soluble fraction is not soluble in conthe use to which the material may be put. Incentrated sulfuric acid, but is soluble in lumasmuch as the amount of tolerance may vary, ins lf ic a g-. containing to P it is desirable to increase it to a point where cent excess S03). The third or insoluble iraccloudiness may be avoided even if relatively large 16 tion is not soluble in either concentrated or fumamounts of the saturates are present in the coning sulfuric acid. It is often a saturated oily deasai'iion protditifit. unreactive hydrocarbon material whicliinis gene ave es a ished, for example, that the un erally similar to the "white oil somet esprosaturated hydrocarbon products obtained from duced from petroleum for medicinal and other waste products of mineral oil refining as de- 20' purposes; scribed in said patent contain or may contain The proportions in which these three consaturated hydrocarbons in variable proportions stituents are present inmhydrocarbon materials ancixihat 'tlzfi presence (if satulgited hyedlrloobtained from petroleum waste products have a car us in eunsa ura e y rocar on ma a1 very definite eiIect on the applicability of such n orpor t d into the resin compositions accord- 3 materials in the synthetic resin arts. Fortunateirigtstgusgid pgtgiit rinag lpgoduce undesirabletrelfy, it is ganteli'allilydgossibe tguietigct or prepare as ou y p arance oro y sur ace ractionso e y ocar on res aving 0 gig; 22 1 1 139 s tpr c s- A1; l object of the desired proportions of the three constituents; and V9 1011 l we have also esti ihii iiiiihes 333; iiofis ilfiiiuiiiiiiilii. fiifiiiifiimflits can be completely eliminated or avoided by obmade by t t t hydrocarbonmixture ob sailvilrggsgeggain rpgzcauti niil 1arm preiautions tained from acid sludge or solvent extract residue scovery con 9115a es with sulfuric acid of about 98 er cent concentaining the unsaturated hydrocarbons previously n ti n This precipitates the ii-st, l bl yg described, and varnishes or other solutons made tl'mt is, the acid dissolves the solublejfmm :2 gggt g g g g z figg gg gsssggf gg' tion and the solution separates from the undisactive hydrocarbons; and that the limit of this solved hydrocarbons' The remaimng part the original material is separated from the solution 1 tolerance or compatibility 1s dependent upon (1) 40 and then treated with fuming sulfuric acid conthe nature of the other constituents of thecondensate; and (2) the amount of theunsaturated Wining from 2,0 to 30 per cent of This prehydrocarbon material. described hereinabove, cmitaftes the second solublefiactioni usually as which is present. This tolerance can also be removed- The remgimngpart modified (that is, increased) to someextent by f the orlginal material is the satumtedunreac' the presence of certain other materials in the tlve material known as the insoluble fraction. condensates or varnishes m'ade therefrom, as dehic O d a y consists of White 011.. solid scribed more fully hereinbelow. parafiin, or both. The saturated hydrocarbon In more detail, we have now found that the material in this insoluble fraction is, for. most essentially unsaturated hydrocarbon material purposes, an impurity in the unsaturated material or the first and second soluble fractions.

bon mixture obtained from acid sludge, there was 80 per cent of the first soluble fraction, per cent of the second soluble fraction and 10 per cent of white oil (the insoluble fraction). Another hydrocarbon mixture, obtained from solvent extract residue, contained 50 per cent of the first soluble fraction, 40 per cent of the sec-- ond soluble fraction, and 10 per cent of white It should be understood that these are merely typical proportions, and that the actual proportions may vary widely in individual cases.

For example, the insoluble fraction may constitute 30 per cent or more of the total hydrocarbon mixture as recovered from petroleum waste products, unless care is taken to minimize it, in which case it may be only 5 per cent or less.

The determination of the composition of the hydrocarbon mixture in terms of these three constituents is often desirable in that it gives considerable additional information as to the character of the materials present. For example, both of the mixtures previously mentioned (obtained from acid sludge and from solvent extract residues, respectively) had iodine numbers of 42 and were generally similar in appearance. However, the first soluble fraction of the product obtained from acid sludge (amounting'to 80 per cent of the total, as noted) had an iodine number of 52, as compared with an iodine number of 72 for the first soluble fraction (50 per cent) of the material obtained from solvent extract residue. The second soluble fractions had iodine numbers of and 12, respectively, while the iodine number of the white 011 was, in both cases, zero.

The amount of white oil which can be tolerated in phenolic condensation products containing these hydrocarbons depends partially, as previously noted, on the type of phenol which is used. This is shown by a series of tests in which a standard formula was employed, varying only the type of phenol, with several diiferent amounts of white oil present. In these tests, the following formula was used:

A phenol (as listed below) --grams-- 100 Formaldehyde (40 per cent solution) do 80 Unsaturated hydrocarbons as described above ams..-

Ammonia (28 per cent solution). ..cc- 6 In preparing the resins, the hydrocarbons were dissolved in the phenol, the formaldehyde was added, and then the ammonia was added. The mixture was refluxed for minutes with good agitation, and then the water and the uncondensed formaldehyde were distilled off under vacuum, until a sample would break in water at 20 C. The resins were tested for clarity by applying a sample to a glass plate, hardening by heating in an oven at 180 C. for 30 minutes, and

observing the resulting film, In a parallel series of tests, the same formula was used, except that 5() parts of the unsaturated hydrocarbons were 'used'instead of the 25 parts (per 100 parts of boiling range of 190 to 220 C,- 4

ll 4 (3), A "commercial cresylic acid" having a higher boiling range of 200 to 240 C.

(4) xylenol.

(5) A mixture of 75 parts high boiling cresylic I acid and 25 parts cresol produced from petroleum sources.

With each phenol, hydrocarbon mixtures containing various amounts of white oil (insoluble fraction) were used, in order to determine the maximum tolerance for white oil of each phenolic condensation product containing 25 or 60 parts of the unsaturated hydrocarbon mixture per 100 parts of phenol. With the first ofthe phenols (from the above list) it was found that a clear resin was obtained only when the hydrocarbons contained a total of 96 per cent of first and second soluble portions-that is, no more than 4 per centof white oil. With the second phenol,

the tolerance for white oil (with 25 to 50 parts of hydrocarbons present per 100 parts of phenol) was 7 per cent of the total hydrocarbons. The results of these tests may be tabulated as follows (the percentage in each case being the maximum permissible percentage of white 011 in the 25 to 50 parts of hydrocarbons employed with each 100 parts of the various phenols, which would permit the attainment of a clear resin film under the described test conditions):

Permissible Percentage of White 011 in Hydrocarbons Phenol No.

It should be noted that the values obtained in these tests relate to hydrocarbon mixtures in which the insoluble portion is white oil. The tolerance for solid paramn is much less than the tolerance for white oil.

These figures indicate the influence of the particular phenol employed on the compatibility of (or tolerance for) white oil in phenol-aldehyde condensation products containing a substantial proportion of the unsaturated hydrocarbons employed in accordance with this invention. When these unsaturated hydrocarbons are omitted. the permissible amount of white 011 falls substantially to zero.

In the foregoing series of tests, a comparison of the resultsobtained with phenol N0. 3 and phenol No. 5 shows that the tolerance for white oil in these phenolic condensation products can be increased substantially by adding certain ingredients to the condensation mixture. In this specific instance, the added ingredient was a cresol of petroleum origin, which is compatible with white oil, and also with the other resin constituents. In addition to this petroleum cresol, other compounds having these characteristics (compatibility with white oil and also with cresol and other resin constituents) may be employed to increase the tolerance of condensates for white oil. Suitable materials of this nature include para-tertiary amyl phenol (also known as amylouble in white oil'than the other compounds men- 5 tioned. The eflectiveness'of addition agents this type is illustrated by tests in which 100 parts of commercial cresol containing 40 per cent of metacresol, 80 parts of formaldehyde (40 per cent solution), 6 parts of ammonia (28 per cent solution), and 25 parts of the unsaturated hydrocarbons containing 20 per cent of white oil were condensed in the manner previously described. As shown hereinabove, the normal tolerance for white oil of a resin made from this phenol is only 4 per cent, on the added hydrocarbons. However, it was found possible to make a clear transparent resin from this formula when employing hydrocarbons containing 20 per cent of white oil by adding one of a) 0.5 to 2 per cent tricresyl phosphate;

(b) 1.5 to 3 per cent para tertiary amyl phenol;

(c) 5 to per cent rosin.

These materials are therefore more effective per unit of weight in making white oil compatible with condensation products than the petroleum cresol used in test No. 5, hereinabove.

The tests described hereinabove, and others of like nature, have established that the compatibility of saturated hydrocarbons or white Oil with phenolic condensation products depends on the kind of phenol used, and may be'modiiied to some extent by the addition of certain agents which are compatible with white oil or with the phenols or with both. It has also been. deter-,

mined that the tolerance for white oils depends largely on the amount of the unsaturated hydrocarbons incorporated in the condensation products in accordance with this invention. In-one demonstration of this, the following tests were made:

250 grams of a commercial cresol for synthetic resin containing per cent of metacres'ol; 200 grams of formaldehyde, 40 per cent solution;

' and 15 cc. of ammonia (28 per cent solution) were condensed by heating under reflux, and water and excess formaldehyde were distilled off until a sample broke in water at 20 C. v The resulting condensation product was mixed with 270 grams methylhexaline (methylcyclohexanol) and the mixture was boiled for one hour to dissolve all of the resin particles. Thirty grams of tung oil dissolved in 135 grams methylhexaline were added to theboiled solution, and the mixture was boiled under reflux at 110 to 130 C. with agitation for about 2 /2 hours. At this time, a clear transparent lacquer base of medium consistencey had been prepared, and it was found that this hardened at 180 C. to an entirely clear film.

This lacquer base was mixed with different amounts of white oil and different amounts of a synthetic mixture of acid soluble (first and second) fractions of the described hydrocarbons. The white oil used was commercial mineral oil having a molecular weight of about 360. Samples represent various proportions of white oil and acid soluble unsaturated hydrocarbons were hardened at 180 C. By the results of this test, it is shown that the tolerance for white oil of this cresol-formaldehyde lacquer is very low, but is substantially increased by increasing the amount of the unsaturated hydrocarbonspresent in accordance with this invention. The results in a typical series of tests are tabulated herewith, in

terms of the maximum percentage (or parts) of 6 white oil which can be tolerated in 100 parts of the above-described lacquer base after adding varying amounts oi acid soluble Naitolen hydro carbons.

Wh te ou- Maximum (Aw: Parts mm) l clcretcd $6 g per 100 parts par Lacquer Lacquer Base Base These results are, of course, specific to the lacquer base made with the stated cresol. As would be expected from the results previously described, the absolute values of the amount of white oil tolerated, in proportion to the amountof unsaturated acid-soluble hydrocarbons present, varies when different phenols are employed. For example, by replacing one-half of this particular cresol with high-boiling cresylic acid, the tolerance for white oil (for a given amount of unsaturated hydrocarbons) is increased' about, 30

per cent over a substantial portion of the range covered.

As shown, the above-mentioned lacquer base tolerates the presence of only about 1.5 per cent -ofwhite oil n the absence of the previouslydeper .cent of paraflin and 9 parts of white on un-- der similar circumstances. The tolerance also differs somewhat for different kinds of white oils. For example, 35 per cent of Russian white oil can sometimes be tolerated in compositions which are made cloudy (in hardened films) by the presence of 30 per cent of American white oil.

We have thus found that improved plastic compositions, and particularly compositions of the phenol-aldehyde type, can be prepared by incorporating in these compositions substantial percentages of an essentially unsaturated hydrocarbon material containing about per cent carbon and 10 per cent hydrogen, which is derived from the waste products of mineral oil refining. We have also found that uniformly satisfactory results can be obtained from such compositions by observing certain precautions involving the amount of saturated hydrocarbons, such as white oil and paraffin, which are incorporated into the condensation products in association with the said unsaturated hydrocarbons. More specifically, we have found that the amount of saturated oils which can be tolerated in phe- -nolic condensation products without causing cloudiness, oil separation, etc., depends (1) on the kind of phenol employed, and (2) on the amount white oils or saturated hydrocarbons. Stated 7 diflerently, our invention thus comprises a method oi incorporating in plastic compositions (and especially those containing phenol-aldecarbon materials not normally compatible with such condensation products; this being eflected without detriment to the properties of the condensation products, and generally resulting in products having improved properties.

Further examples of condensation products hyde condensation products) saturated hydroand their production within the scope of this invention are as follows:

Example A P Cresylic ac'i with a boiling range 199 to The above-described unsaturated hydrocarbons containing 8% white oil 25 Formaldehyde (40% solution) 95 Ammonia (28% solution) a These ingredients were condensed, and the uncondensed parts (e. g., water and excess iormaldehyde) were distilled oil in the usual manner. After reaching the stage at which the resin sample became brittle it tested in water at 20 0., the melted resin in the kettle was dissolved in 80 parts of solvent mixture composed of 40 parts of toluene and 40 parts of ethyl alcohol. An excellent laminating varnish was thus obtained.

Example B Parts Cresol with 40% meta-cresol 100 Formaldehyde (40% solution) 90' The unsaturated hydrocarbons containing 8-16 parts of white oil 20-50 Ammonia (28% solution) 10 were condensed, and the uncondensed parts were distilled oil in the usual manner. After the resin samples tested in water showed the characteristic brittleness, 50 parts of methyl cyclohexanol were added and the resin solution was heated under reflux at about 120 C. for a few hours until a sample showed the viscosity of a very heavy honey. The resulting liquid resin was further diluted with 60 parts of a mixture composed of 30 parts toluene and 30 parts alcohol. This product is well adapted for use in laminating operations, has a short curing time, and shows excellent electrical properties. Slight cloudiness, etc., is sometimes encountered when using hydrocarbons containing the larger amounts or white oil; and if this is objectionable, it is readily overcome by including in the condensation mixture arts Example D Parts by weight Cresylic acid from petroleum sources 100 Formaldehyde (40% solution) 80 The above-described unsaturated hydrocarbons with 0-20% of white oil -50 Ammonia (28% solution) 6 These ingredients, when condensed and distilled in the usual manner, yielded a clear, hard thermoplastic (not thermo-setting) resin useful in varnishes. It was easily soluble in drying oils, including China-wood oil and linseed oil.

Example E Parts by weight men boiling xylenol 100 The above-described unsaturated hydrocarbons containing 846% 01' white oil 25-50 Formaldehyde (40% solution)-.. 100

These ingredients were condensed without any accelerator, anddistilled in the normal manner. The resulting liquid, thermo-setting resin was used to impregnate fabrics and asbestos, then hardened'by heating or molding to produce articles having excellent chemical resistance.

. The unsaturated hydrocarbon materials used in the foregoing examples-were produced from acid sludge and from the residues or solvent extract refining of mineral lubricating oils. In order to reduce the white oil content of these hydrocarbone to the desired range, the acid sludge used as a starting material in some cases was centriiuged prior to processing in accordance with the procedures previously mentioned. The hydrocarbons derived from solvent extracts were selected from fractions having the desired contents of first and second acid soluble portions. In selecting these fractions, it is merely necessary to iractionate a sample of an unsaturated hydrocarbon mixture produced as described heretofore, and to test the fractions to ascertain their one of the compatible modifying agents mentioned hereinabove, such as para tertiary amyl phenol or rosin.

Example C Parts Cresylic acid with a boiling range of 180 to 210 C '75 Cresyllc acid made from petroleum sources 25 Formaldehyde (40% solution) 90 Ammonia (28% solution) 8 The above-described unsaturated hydrocarbons with 16 parts 01' white oil 25 These ingredients were condensed and distilled in the described manner, and diluted with 80 per cent of a mixture containing 40 parts or toluene and 40 parts of alcohol to make an excellent Y laminating varnish. Before diluting with the solvent mixture. there is obtained a resin which is well adapted for lacquer purposes.

contents of first and secondsoluble portions and insoluble portions. main body of the hydrocarbon mixture is iractionated to obtain products having the desired phenol condensible therewith to form a heathardenable resin,-unsaturated hydrocarbons capable or condensing therewith, a proportion of more than 4% of saturated hydrocarbons boiling in the range of to 360 C. at 12 mm. Hg, and sufllcient to cause substantial cloudiness when said resin is hardened, and rosin, the

amount of rosin being less than 10%,said unsaturated hydrocarbons being derived from byproducts or mineral oil refining of the class consisting of those obtained byneutralizing petroleum acid sludge and iractionating the organic constituents thereof under vacuum to eliminate at least the portions boiling outside the range With this information, the

from 160' to 360 c. at.12 mm. Hg, and those obtained as solvent extract residues in the selec-" tive solvent refining mineral oils, said unsaturated hydrocarbons having a composition of approximately 90% carbon and 10% hydrogen.

2. A heat-hardenable synthetic resin'composition or the phenol-aldehyde type containing saturated hydrocarbons in an amount sufllcient to cause cloudiness when hardened, said resin having the characteristic of being substantially free from cloudiness when hardened, comprising a heat-hardenable condensate of a mixture of a phenol, said phenol being condensable with formaldehyde to form a heat-hardenable resin, formaldehyde and unsaturated hydrocarbon and a proportion of more than 4% 01' saturatedhydrocarbons boiling in the range of 160 to 360 C. at 12 mm. Hg, said proportion of said saturated hydrocarbons being sufilcient to cause substantial cloudiness in the said resin when hardened, and rosin, the amount of resin being less than 10%,

said unsaturated hydrocarbons being derived from bar-products of mineral oil refining of the class consisting of those obtained'by neutralizing petroleum acid sludge and fractionating the organic constituents thereof under vacuum to eliminate at least the portions boiling outside the range from 160' to 360 C. at 12 mm. Hg, and those obtained as solvent extract residues in the selec tive solvent refining of mineral oils, said unsaturated hydrocarbons having a composition of approximately carbon and 10% hydrogen.

FRITZ ROS'I'LER. LEOPOLD BORNSTEIN.

REFERENCES CITED The following references are of recordin the file of this patent:

UNITED STATES PATENTS 

